CN109767922A - A kind of layer zinc oxide light anode structure and photovoltaic application - Google Patents
A kind of layer zinc oxide light anode structure and photovoltaic application Download PDFInfo
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Abstract
The present invention provides a kind of two-layer composite ZnO photo-anode preparation methods, not only preparation method is simple, more importantly this structure has given full play to the advantage of two kinds of ZnO structures respectively, it can be complementary to one another again, make light anode electron-transport, light scattering, mechanical adhesion, electrolyte osmosis, in terms of all have excellent performance, the dye-sensitized solar cells based on this light anode is significantly improved in terms of battery performance.
Description
Technical field
The invention belongs to new energy materials and devices field, and in particular to a kind of layer zinc oxide light anode preparation method.
Background technique
Zinc oxide (ZnO) is a kind of typical II-VI group metal oxide, molecular weight 81.37, density 5.606gcm-
3,1975 DEG C of fusing point, 2360 DEG C of boiling point.Common ZnO crystal structure be hexagonal wurtzite structure and cubic sphalerite structure,
In, the ZnO of wurtzite structure is more stable.As a kind of typical direct band gap N-type semiconductor material, ZnO is at normal temperature
Forbidden bandwidth is 3.37eV, similar to GaN forbidden bandwidth, while its exciton binding energy is up to 60meV, is much larger than zinc selenide
(ZnSe), the semiconductor materials such as GaN, therefore there is important application value.In addition, ZnO has special conduction, thermal conductivity
Can and good biocompatibility, in addition material source very abundant, therefore there is great application value.With Material growth
Technique and substantially development, ZnO has shown excellent performance in numerous areas, such as transparent electrode, ultraviolet detector, hair
Optical diode, solar battery, supercapacitor, nano generator, stress strain gauge, gas sensor, bio-sensing
Device etc..
Dye-sensitized solar cells (DSCs) are a kind of novel solar batteries developed by imitating photosynthesis.
DSCs is a kind of representative third generation photovoltaic technology, and core operating principle is to carry out light absorption using dye molecule,
The separation and collection that photogenerated charge is carried out using semiconductor material, are finally converted solar energy into electrical energy.DSCs has following excellent
Point: abundant raw materials, at low cost, technology is relatively easy, has great advantages in large area industrialized production, simultaneously
All raw material and production technology are all nontoxic, free of contamination, the available sufficient recycling of some materials, to protection mankind's ring
Border has great importance.From Lausanne, SUI federation science and engineering (EPFL) in 1991The research group of leader is taught in the skill
Since making a breakthrough in art, Europe, the United States, Deng developed country investment substantial contribution are used for the research and development of DSCs.Core as DSCs
Component part, light anode play decisive role to battery performance.Effect of the light anode in DSCs is predominantly adsorbed dyestuff, is received
Collect and transmits light induced electron.Currently, most common two kinds of optical anode materials be titanium oxide (TiO2) with anatase crystal and
Zinc oxide (ZnO) with wurtzite phase, two kinds of materials have comparable band gap width, but ZnO is in electron-transport and shape
Looks regulation aspect more has advantage.ZnO-DSCs is also referred to as by the dye-sensitized solar cells of light anode of ZnO.It is right
ZnO photo-anode development table/modifying interface and Morphological control are the effective ways for promoting ZnO-DSCs performance.For example, Greece
Maria Vasilopoulou et al. once carried out moditied processing to the surface ZnO using air and water vapour low temperature plasma, removed
The extra positive charge for having gone to the surface ZnO to cover reduces Zn2+The formation probability of/dyestuff cluster, to effectively increase electron injection
Efficiency and battery efficiency.In addition, some researchers propose to provide effective channel using complex light anode for the fast transferring of electronics,
Electron transfer rate is improved, separation of charge ability is reinforced, improves battery performance.Xu such as Southeast China university et al. uses graphite
Alkene is compound with ZnO, effectively extends the light induced electron service life, reduces interior resistance, has obtained 5.86% photoelectric conversion efficiency.More
More researchers is studied from light anode micro-nano structure design, so as to improve battery performance.In recent years, researcher
By synthesizing the ZnO nano material with various abundant novel patterns, (such as nano flower is received as stick, nanocluster, nano-array
Deng) as light anode come increase material specific surface area, increase Dye Adsorption amount, widen light abstraction width, always improve luminous energy
Utilization rate.The nanometer sea urchin structure synthesized such as the Xia Tao study group of Beijing University of Chemical Technology using hydro-thermal method obtains 6.40% photoelectricity
The efficiency of ZnO is increased to 6.42% using multistage cluster structure by transfer efficiency, Ma Tingli study group, Dalian University of Technology.
More and more evidences show that three-dimensional multistage structure is a kind of ideal optical anode material.ZnO three-dimensional multistage
Structure generally includes primary structure and secondary structure, wherein primary structure is basic structural unit, can be nanoparticle, receives
Rice noodles or nanometer sheet etc.；Primary structure is assembled according to specific spatial arrangement mode, so as to form larger-sized time
Level structure, such as spheroidal aggravation, flower-shaped aggregation, tree-shaped aggregation or sheet aggregation etc..Have with those simple
One-dimensional or two-dimensional structure nanometer light anode is different, and the light anode of three-dimensional multistage structure can play primary and secondary knot simultaneously
Photoelectric properties are substantially improved with this in the advantage of structure.2008, Zhang et al. synthesized diameter using the method for solvent heat and has existed
The ZnO ball aggressiveness of 200nm or so, the structure are reunited by the ZnO little particle that partial size is more than ten nanometers.The knot of this bulb aggressiveness
Structure advantage is embodied in: the primary structure of small size makes material have up to 80m2g-1Specific surface area, can fully ensure that
Light anode can adsorb more dye molecule；Secondary structure has suitable size, can sufficiently scatter sunlight, this just prolongs
The transmission range for having grown photon is conducive to the capture of photon.The result shows that being prepared into porous electrode by the structure with a thickness of 10
μm, using N3 dyestuff and liquid electrolyte, the efficiency of battery reaches 5.4%.In addition, Shi et al. synthesized and
Nanometer sheet composition ZnO multilevel structure, this structure other than with biggish specific surface area and good light scattering property,
Express passway can also be provided for the transmission of electronics, finally, the ZnO-DSCs photoelectric conversion efficiency prepared has reached 6% or more.
Using ZnO multilevel structure although higher photoelectric conversion efficiency can be obtained, this structure since size is larger,
Contact with conductive substrates is poor, is easy to fall off from conductive substrates, this to the stability of battery be it is unfavorable, this is multistage knot
Structure is used as the greatest problem that DSCs light anode faces.Therefore, we must design a kind of novel light anode structure, can play
The advantage of multilevel structure, while can solve the problem of it is easy to fall off again.
Summary of the invention
To solve the problems mentioned above in the background art.The present invention provides a kind of layer zinc oxide light anode preparation sides
Method.
To achieve the above object, the invention provides the following technical scheme: a kind of layer zinc oxide light anode, wherein bottom knot
Structure is ZnO nanoparticle, and upper layer is micron-sized ZnO multilevel structure.
The synthetic method of ZnO nanoparticle is polishing, and temperature is room temperature, and specific preparation process is as follows:
(1) zinc salt solid is mixed with strong basic solid and grinds to obtain the white paste of fine particle；
(2) paste is collected into plastic tube, and a certain amount of deionized water is added thereto, shake up rear room temperature ageing
For a period of time；
(3) a certain amount of deionized water is added in the white paste being aged in step (2), and is used in ultrasound again
Concussion and whirlpool concussion are dispersed, are washed, and place after washing, supernatant liquor is gone, wash repeatedly, until supernatant liquor PH
Value reaches neutral；
(4) white precipitate finally obtained in step (3) is centrifuged；
(5) a certain amount of ionized water is added in the ZnO nanoparticle that step (4) is centrifugally separating to obtain again, is shaken in ultrasound
It swings and disperses under conditions of being shaken with vortex to get 1#ZnO slurry is arrived.
In the step (1), zinc salt is one of zinc chloride, zinc nitrate, zinc sulfate, zinc acetate, and highly basic is hydroxide
Sodium or potassium hydroxide, zinc salt mass ratio are 2:3~6；
In the step (2), the ratio between deionized water volume and paste volume of addition are 0.5~2:1, and digestion time is
10~for 24 hours；
In the step (3), deionized water quality is 5~10 times of paste quality, ultrasonic vibration frequency is 35~
45KHz, time are 5~10 minutes, and whirlpool oscillation frequency is 400~600Hz, and the time is 3~5 minutes；
In the step (5), the deionized water quality of addition is 4~8 times of white solid quality；ZnO nanoparticle exists
Dispersion is carried out under conditions of ultrasonic vibration and vortex shake in deionized water, the frequency of the ultrasonic vibration is 35~
45KHz, time are 5~10 minutes, and the frequency of vortex concussion is 400~600Hz, and the time is 3~5 minutes, the time is 3~
It 5 minutes, is repeated 5 times altogether.
Micron-sized ZnO multilevel structure synthetic method is ultrasonic wave added coprecipitation, and temperature is room temperature, specific preparation step
It is as follows:
(1) it prepares certain density strong alkali aqueous solution and zinc salt solution, strong base solution is transferred in beaker, stirred in machinery
It mixes and stirs under ultrasonic collective effect, zinc salt solution is added thereto, later stand reactant, white precipitate can be obtained；
(2) precipitating in step (1) is filtered, later with deionized water dispersion, washing, filtering, obtains ZnO multilevel structure
Solid；
(3) a certain amount of ZnO multilevel structure solid is weighed, a certain amount of ZnO nanoparticle is added, body is added after mixing
Product is dispersed by the way of ultrasound plus concussion later than the mixed solvent for the second alcohol and water for being 1:1, finally obtains 2# slurry
Material.
Highly basic in the step (1) is sodium hydroxide or potassium hydroxide, and zinc salt is zinc nitrate hexahydrate, zinc chloride, first
Sour zinc or Zinc diacetate dihydrate, wherein the concentration of lye be 0.50~1.50mol/L, zinc solution concentration be 0.10~
0.50mol/L；
In the step (1), strong base solution is identical with zinc solution volume, the drop rate of zinc solution be 1ml/s~
10ml/s；
In the step (1), ultrasonic frequency is 20KHz~80KHz, and stirring rate is 200rpm~600rpm, ultrasound
Time with stirring is 10min, time of repose 4h；
In the step (2), the deionized water volume for washing is 30~80ml, and dispersion adds whirlpool using ultrasonic vibration
Mixing concussion, ultrasonic vibration frequency are 35~45Hz, and the time is 5~10 minutes, and whirlpool oscillation frequency is 18~22Hz, and the time is
3~5 minutes；
In the step (3), in 2# slurry, the mass ratio of ZnO multilevel structure and ZnO nanoparticle be 4:0.5~
1.5；
In the step (3), 4~6:1 of mass ratio of mixed solvent and ZnO solid；
In the step (3), in dispersion process, supersonic frequency 40KHz, the time is 5 minutes, and whirlpool oscillation frequency is
600Hz, time are 5 minutes；Ultrasound and concussion dispersion process are repeated 4 times.
It is a further object to provide a kind of preparation methods of layer zinc oxide light anode, the specific steps are as follows:
(1) 1# slurry is scratched in clean conductive substrates, controls film thickness using the ultra-thin adhesive tape of polyimides, scrapes
Film placement is placed the regular hour in air after the completion of painting, film is kept to be in leather hard；
(2) it is further added by adhesive tape on the basis of original adhesive tape, scratches reality 2# slurry later；After the completion of blade coating, sample is put
Then naturally dry in air places into baking oven and heats, be cooled to room temperature later；
It (3) is 0.1~0.8mmol L in concentration by the light anode through Overheating Treatment-1Dye solution in impregnate 60~180
Minute, the dye solution is N719 dye solution；
(4) coat gel electrolyte in the light anode after sensitization, heel be superimposed together to electrode, fixed with clip
After be put into baking oven and heat, finally complete the assembling of device.
The conductive substrates of solar battery light anode in the step (1) are FTO glass；
Tape thickness is 20~40 μm in the step (1), after knifing is completed time for placing in air be 5~
15min；
Increase in the step (2) adhesive tape with a thickness of 40~80 μm, 200~300 DEG C of heat treatment temperature, 2~4h of time；
Electrolyte used in the step (4) has following composition: 0.1mol L-1LiI, 0.1mol L-1I2,
0.6mol L-11,2- dimethyl -3- propyl imidazole iodine, 0.45mol L-1N- methyl sheet and imidazoles, solvent is methoxy propyl
Nitrile, gelling agent are polyethylene oxide, and additive amount is the 10% of liquid electrolyte quality；
In the step (4), gel electrolyte needs first to carry out the pre-heat treatment before coating, it is therefore an objective to make it have certain
Mobility, heating temperature be 50~90 DEG C；Light anode is 80~100 DEG C with the heat treatment temperature after overlapping to electrode, when
Between 15~30 minutes, the purpose for the arrangement is that in order to permeate gel electrolyte completely in porous electrode.
Preparation ZnO superfine nano chip architecture, preparation method and light anode provided by the invention have the following aspects
The advantages of: (1) synthetic method of this ZnO superfine nano piece under normal temperature conditions carry out, by hydroxide solids and zinc
Salt solid mixed grinding in agate mortar can be prepared by, and experimental implementation is simple, rapid reaction, raw material are cheap and easy to get；
(2) reaction process of ZnO superfine nano piece does not need organic solvent participation, and the development for meeting Green Chemistry is newly wanted
It asks, has the advantages that environmental-friendly；
(3) the ZnO superfine nano piece based on above method preparation is applied in dye-sensitized solar cell anode, this
The heat treatment operation of kind photo-anode film does not need too high temperature, can carry out at 200 DEG C, therefore is relatively suitble to prepare soft
Property solar cell device；
(4) photo-anode film of method preparation is that the irregular nanometer sheet being crossed-over is formed, and is had preferable
Cellular structure and good electric conductivity, preparation process do not need additionally to add organic pore-forming agents, this similar sponge it is porous
The porosity with higher of light anode made of structure and optical density, cellular structure are conducive to the infiltration of quasi-solid electrolyte.
The invention has the following beneficial effects:
The present invention provides a kind of simple, green, efficient, low cost and the methods for being easily achieved magnanimity preparation, by this
Method can prepare ZnO superfine nano piece in irregular shape.This superfine nano piece can form hole by mutually accumulation
The excellent ZnO photo-anode of structure realizes low temperature preparation so as to avoid the addition and Severe Thermal Ageing process of pore creating material.?
In this light anode, the quick transmission of electronics, spongiform porous structure is may be implemented in the crosslinking interworking architecture between nanometer sheet
Big specific surface area is provided, is conducive to adsorb more dye molecules, this is to acquisition high-performance ZnO radical dye sensitization solar
Battery provides important thinking.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the SEM photograph for the sample that embodiment 1 synthesizes, wherein (a) and (b) figure are that the ZnO that polishing is prepared receives
Rice grain, (c) and (d) figure is flower-like structure ZnO micron particles；
Fig. 2 is the photo-anode film section SEM photograph based on ZnO micron particles that embodiment 2 is prepared；
Fig. 3 is the composite structure light anode film sections SEM photograph that embodiment 3 is prepared；
Fig. 4 is the DSCs current-voltage scanning curve that embodiment 4 is prepared；
Fig. 5 is the DSCs current-voltage scanning curve that embodiment 5 is prepared；
Fig. 6 is the DSCs current-voltage scanning curve that embodiment 6 is prepared；
Fig. 7 is the DSCs ac impedance measurement in embodiment 4,5,6 as a result, wherein (a) is Nyquist figure, and (b) figure is to hand over
The electron lifetime result obtained after flow impedance result treatment.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
The present embodiment is two kinds of ZnO samples required for preparing composite structure light anode, and one kind is ZnO nanoparticle, separately
It is a kind of for the micron order ZnO particle with multilevel structure.
6g sodium hydroxide and 8g zinc chloride solid are weighed, is put into mixed grinding in agate mortar, milling time 20min,
Obtain white paste；Paste is transferred in plastic centrifuge tube to and is added 30ml deionized water, stands 2h after shaking up；It outwells
Supernatant retains the white precipitate of centrifugation bottom of the tube；40ml deionized water is added in Xiang Guanzhong, shakes item in ultrasonic vibration and whirlpool
Precipitating is washed under part, ultrasonic vibration frequency is 40KHz, and time 5min, the frequency of whirlpool concussion is 600Hz, time 3min；
Then precipitating is centrifuged, and centrifuge separation revolution is 3000r/min, time 10min；Alternately washing of precipitate and from
Heart lock out operation, is repeated 5 times altogether.By the white precipitate of acquisition, 20ml deionized water is added, is shaken in ultrasonic vibration and vortex
Under the conditions of carry out mixing dispersion, the frequency of ultrasonic vibration is 40KHz, time 10min, and the frequency of the vortex concussion is
600Hz, time 5min, is repeated 5 times altogether, obtains 1# zinc oxide slurry.
It prepares each 1L of sodium hydroxide solution of the liquor zinci chloridi and 1mol/L of 0.5mol/L respectively with volumetric flask, then will
Alkaline solution is transferred in the beaker of 2.5L, is put into agitating paddle and is carried out mechanical stirring；Slowly add into above-mentioned sodium hydroxide solution
Enter liquor zinci chloridi, it is about 35ml/s, ultrasonic disperse frequency 50KHz, duration 40s that rate, which is added,；Ultrasound will after stopping
Reaction system stands 3h, filters out supernatant liquid later, and deionized water is then added and continues to wash, until the pH of supernatant liquor
It until value is neutral, is finally washed with dehydrated alcohol, and in 70 DEG C of at a temperature of drying, obtains white solid powder.
As shown in Figure 1, the sample prepared of polishing is ZnO superfine nano particle, size wider distribution, but generally several
Ten nanometers or less；The sample prepared with ultrasonic wave added coprecipitation is micron-sized flower-shaped multilevel structure, the multilevel structure by
Nanometer sheet composition, has macroporous structure abundant.
Embodiment 2
The present embodiment is to show the physical contact between micron-sized ZnO multilevel structure and FTO substrate.
The flower-shaped multilevel structure of ZnO synthesized in 0.8 gram of embodiment 1 is weighed, is added containing in 0.2 gram of embodiment 1
The mixed solvent (volume ratio 1:1) of 4 grams of second alcohol and waters is added in the ZnO nanoparticle synthesized after mixing, later using ultrasound
The mode of+concussion is dispersed, wherein supersonic frequency 40KHz, time are 5 minutes, shake and shake for whirlpool, frequency is
600Hz, time are 5 minutes；Ultrasound and concussion dispersion process are repeated 4 times, obtain 2# slurry.The 2# slurry prepared is scraped
It is coated on clean FTO electro-conductive glass, film thickness is controlled using the ultra-thin adhesive tape with a thickness of 70 μm, by film after the completion of blade coating
Naturally dry in air is placed, is put into heating, drying in baking oven later, temperature is 200 DEG C, time 2h.
The photo-anode film prepared is scanned Electronic Speculum (SEM characterization), as shown in Figure 2.It can be seen that from (a) figure
The thickness of film is about 30 μm, can be seen that the physical contact area between micron-sized ZnO multilevel structure and substrate from (b) figure
Smaller, contact is poor, and film is easy to cause to split away off from FTO.
Embodiment 3
The present embodiment is the structure in order to show the photo-anode film with micro-nano two-layer composite.
By the 1# slurry prepared in embodiment 1 blade coating in clean conductive substrates, the ultra-thin adhesive tape of polyimides is used
Film thickness is controlled, tape thickness is 30 μm；Film is placed after the completion of blade coating and is placed 10 minutes in air, at this point, in original
Have and be further added by the adhesive tape that a layer thickness is 50 μm on the basis of 30 μm of adhesive tapes, so that the overall thickness of adhesive tape is become 80 μm, scratch later
2# slurry in embodiment 2；After the completion of blade coating, sample is put into naturally dry in air, then places into baking oven and heats, heat
250 DEG C for the treatment of temperature, time 4h.
The photo-anode film prepared is subjected to SEM characterization, as a result as shown in Figure 3.Firstly, from figure (a) as can be seen that should
Light anode has apparent double-layer structure, and bottom is ZnO nano particle, comparatively dense, and upper layer is micron-sized ZnO multilevel structure
Nano particle contacted with FTO substrate it is very abundant, meanwhile, micron-sized ZnO multilevel structure is trapped in bottom, is had for two layers
Adequately physical contact.
Embodiment 4
The present embodiment is the photoelectric properties in order to investigate the light anode of simple ZnO nanoparticle composition.
By the 1# slurry prepared in embodiment 1 blade coating in clean conductive substrates, the ultra-thin adhesive tape of polyimides is used
Film thickness is controlled, tape thickness is 30 μm；Film is placed after the completion of blade coating and is placed 10 minutes in air.Then it places into
It is heated in baking oven, 250 DEG C of heat treatment temperature, time 4h.The ZnO photo-anode prepared is preheated at 80 DEG C first, is put into later
(concentration is 0.5mmol L in N719 dye solution-1) sensitization 2h, the dye solution is N719 dye solution cis-bis
(isothiocyanato)bis-(2,2'-bipyridyl-4,4'-dicarboxylato)–ruthenium(II)bis-
tetrabutylammonium.Gel electrolyte, gel electrolyte composition are as follows: 0.1mol are coated in light anode after sensitization
L-1LiI, 0.1mol L-1I2,0.6mol L-11,2- dimethyl -3- propyl imidazole iodine, 0.45molL-1N- methyl sheet
And imidazoles, solvent are methoxypropionitrile, gelling agent is polyethylene oxide (molecular weight 2,000,000), and additive amount is liquid electrolyte matter
The 10% of amount.Be coated with gel electrolyte light anode be coated with being superimposed together to electrode for Pt, fixed with clip, later
It is put into baking oven and heats, heating temperature is 85 DEG C, and device is taken out test later by heating time 30min.
It can be calculated, be opened a way using the DSCs that 1# slurry is prepared electric from the current-voltage scanning curve in Fig. 4
Pressure, short circuit current, fill factor and photoelectric conversion efficiency are respectively as follows: 0.71V, 6.56mA cm-2,0.67,3.15%.
Embodiment 5
The present embodiment is the photoelectric properties in order to investigate the light anode of simple ZnO multilevel structure composition.
By the 2# slurry prepared in embodiment 2 blade coating in clean conductive substrates, the ultra-thin adhesive tape of polyimides is used
Film thickness is controlled, tape thickness is 50 μm；Film is placed after the completion of blade coating and is placed 10 minutes in air.Then it places into
It is heated in baking oven, 250 DEG C of heat treatment temperature, time 4h.The ZnO photo-anode prepared is preheated at 80 DEG C first, is put into later
(concentration is 0.5mmol L in N719 dye solution-1) sensitization 2h, the dye solution is N719 dye solution cis-bis
(isothiocyanato)bis-(2,2'-bipyridyl-4,4'-dicarboxylato)–ruthenium(II)bis-
tetrabutylammonium.Gel electrolyte, gel electrolyte composition are as follows: 0.1mol are coated in light anode after sensitization
L-1LiI, 0.1mol L-1I2,0.6mol L-11,2- dimethyl -3- propyl imidazole iodine, 0.45mol L-1N- methyl
Simultaneously imidazoles, solvent are methoxypropionitrile for this, and gelling agent is polyethylene oxide (molecular weight 2,000,000), and additive amount is liquid electrolyte
The 10% of quality.Be coated with gel electrolyte light anode be coated with being superimposed together to electrode for Pt, fixed with clip, it
After be put into baking oven and heat, heating temperature is 85 DEG C, and device is taken out test later by heating time 30min.
It can be calculated, be opened a way using the DSCs that 1# slurry is prepared electric from the current-voltage scanning curve in Fig. 5
Pressure, short circuit current, fill factor and photoelectric conversion efficiency are respectively as follows: 0.70V, 11.63mA cm-2,0.65,5.30%.
Embodiment 6
The present embodiment is the photoelectric properties in order to investigate double-layer structure light anode.
By the 1# slurry prepared in embodiment 1 blade coating in clean conductive substrates, the ultra-thin adhesive tape of polyimides is used
Film thickness is controlled, tape thickness is 30 μm；Film is placed after the completion of blade coating and is placed 10 minutes in air, at this point, in original
Have and be further added by the adhesive tape that a layer thickness is 50 μm on the basis of 30 μm of adhesive tapes, so that the overall thickness of adhesive tape is become 80 μm, scratch later
2# slurry in embodiment 2；After the completion of blade coating, sample is put into naturally dry in air, then places into baking oven and heats, heat
250 DEG C for the treatment of temperature, time 4h.The ZnO photo-anode prepared is preheated at 80 DEG C first, is put into N719 dye solution later
(concentration is 0.5mmol L-1) sensitization 2h, the dye solution is N719 dye solution cis-bis (isothiocyanato)
bis-(2,2'-bipyridyl-4,4'-dicarboxylato)–ruthenium(II)bis-tetrabutylammonium。
Gel electrolyte, gel electrolyte composition are as follows: 0.1mol L are coated in light anode after sensitization-1LiI, 0.1mol L-1's
I2,0.6mol L-11,2- dimethyl -3- propyl imidazole iodine, 0.45mol L-1N- methyl sheet and imidazoles, solvent is methoxy
Base propionitrile, gelling agent are polyethylene oxide (molecular weight 2,000,000), and additive amount is the 10% of liquid electrolyte quality.It is being coated with
The light anode of gel electrolyte be coated with being superimposed together to electrode for Pt, fixed with clip, be put into baking oven heat later, added
Hot temperature is 85 DEG C, and device is taken out test later by heating time 30min.
It can be calculated from the current-voltage scanning curve in Fig. 6, the DSCs based on two-layer composite light anode is opened
Road voltage, short circuit current, fill factor and photoelectric conversion efficiency be respectively as follows: 0.70V, 13.99mA cm-2,0.69,
6.80%.It can be seen that the photoelectric properties of battery are obviously improved after using two-layer composite light anode.
Embodiment 7
The present embodiment is the internal physical process in order to characterize device by ac impedance measurement.
DSCs device in embodiment 4,5,6 is subjected to ac impedance measurement, frequency range under different bias conditions
For 0.05Hz~1MHz.The battery device compared first has used ZnO multilevel structure light anode (to refer in particular to " multistage in figure respectively
Structural membrane ") and two-layer composite light anode (refering in particular to " laminated film " in figure), the Nyquist figure of battery device is by two
A semicircle composition, first semicircle are located at high frequency region, and the information of display is transfer impedance；Second semicircle is located at middle low frequency range,
The composite impedance of display.There is lesser transfer impedance and bigger compound by scheming composite structure light anode it can be seen from (a)
Impedance, this is conducive to the fast transfer of electronics and effectively collects.From figure (b) as can be seen that using the battery of compound structure film
With longer electron lifetime, be conducive to the collection of electronics.
Claims (7)
1. a kind of layer zinc oxide light anode, which is characterized in that wherein fabric is ZnO nanoparticle, and upper layer is micron order
ZnO multilevel structure.
2. layer zinc oxide light anode according to claim 1, it is characterised in that: the synthetic method of ZnO nanoparticle is
Polishing, temperature are room temperature, and specific preparation process is as follows:
(1) zinc salt solid is mixed with strong basic solid and grinds to obtain the white paste of fine particle；
(2) paste is collected into plastic tube, and a certain amount of deionized water is added thereto, shaken up rear room temperature and be aged one section
Time；
(3) a certain amount of deionized water is added in the white paste being aged in step (2), and is used in ultrasonic vibration again
Dispersed with whirlpool concussion, washed, placed after washing, supernatant liquor is gone, washed repeatedly, until supernatant liquor pH value reaches
To neutrality；
(4) white precipitate finally obtained in step (3) is centrifuged；
(5) a certain amount of ionized water is added in the ZnO nanoparticle that step (4) is centrifugally separating to obtain again, in ultrasonic vibration and
Disperse under conditions of vortex concussion to get 1#ZnO slurry is arrived.
3. layer zinc oxide light anode according to claim 2, it is characterised in that: in the step (1), zinc salt is chlorination
One of zinc, zinc nitrate, zinc sulfate, zinc acetate, highly basic be sodium hydroxide or potassium hydroxide, zinc salt mass ratio be 2:3~
6；
In the step (2), the ratio between deionized water volume and paste volume of addition be 0.5~2:1, digestion time be 10~
24h；
In the step (3), deionized water quality is 5~10 times of paste quality, and ultrasonic vibration frequency is 35~45KHz,
Time is 5~10 minutes, and whirlpool oscillation frequency is 400~600Hz, and the time is 3~5 minutes；
In the step (5), the deionized water quality of addition is 4~8 times of white solid quality；ZnO nanoparticle go from
Dispersion is carried out under conditions of ultrasonic vibration and vortex shake in sub- water, and the frequency of the ultrasonic vibration is 35~45KHz,
Time is 5~10 minutes, and the frequency of the vortex concussion is 400~600Hz, and the time is 3~5 minutes, and the time is 3~5 minutes,
It is repeated 5 times altogether.
4. layer zinc oxide light anode according to claim 1, it is characterised in that: micron-sized ZnO multilevel structure synthesis
Method is ultrasonic wave added coprecipitation, and temperature is room temperature, and specific preparation process is as follows:
(1) prepare certain density strong alkali aqueous solution and zinc salt solution, strong base solution be transferred in beaker, in mechanical stirring and
Under ultrasonic collective effect, zinc salt solution is added thereto, later stands reactant, white precipitate can be obtained；
(2) precipitating in step (1) is filtered, later with deionized water dispersion, washing, filtering, it is solid obtains ZnO multilevel structure
Body；
(3) a certain amount of ZnO multilevel structure solid is weighed, a certain amount of ZnO nanoparticle is added, volume ratio is added after mixing
For the mixed solvent of the second alcohol and water of 1:1, is dispersed by the way of ultrasound plus concussion later, finally obtain 2# slurry.
5. layer zinc oxide light anode according to claim 4, it is characterised in that:
Highly basic in the step (1) is sodium hydroxide or potassium hydroxide, and zinc salt is zinc nitrate hexahydrate, zinc chloride, zinc formate
Or Zinc diacetate dihydrate, wherein the concentration of lye is 0.50~1.50mol/L, and zinc solution concentration is 0.10~0.50mol/
L；
In the step (1), strong base solution is identical with zinc solution volume, and the drop rate of zinc solution is 1ml/s~10ml/
s；
In the step (1), ultrasonic frequency be 20KHz~80KHz, stirring rate be 200rpm~600rpm, ultrasound and stir
The time mixed is 10min, time of repose 4h；
In the step (2), the deionized water volume for washing is 30~80ml, and dispersion adds whirlpool to mix using ultrasonic vibration
Concussion, ultrasonic vibration frequency are 35~45Hz, and the time is 5~10 minutes, and whirlpool oscillation frequency is 18~22Hz, and the time is 3~5
Minute；
In the step (3), in 2# slurry, the mass ratio of ZnO multilevel structure and ZnO nanoparticle is 4:0.5~1.5；
In the step (3), 4~6:1 of mass ratio of mixed solvent and ZnO solid；
In the step (3), in dispersion process, supersonic frequency 40KHz, the time is 5 minutes, and whirlpool oscillation frequency is
600Hz, time are 5 minutes；Ultrasound and concussion dispersion process are repeated 4 times.
6. a kind of preparation method of layer zinc oxide light anode, which is characterized in that specific step is as follows:
(1) 1# slurry is scratched in clean conductive substrates, controls film thickness using the ultra-thin adhesive tape of polyimides, scrapes and be painted with
Film placement is placed the regular hour in air after, film is kept to be in leather hard；
(2) it is further added by adhesive tape on the basis of original adhesive tape, scratches reality 2# slurry later；After the completion of blade coating, sample is placed on sky
Naturally dry in gas, then places into baking oven and heats, and is cooled to room temperature later；
It (3) is 0.1~0.8mmol L in concentration by the light anode through Overheating Treatment-1Dye solution in impregnate 60~180 points
Clock, the dye solution are N719 dye solution；
(4) coat gel electrolyte in the light anode after sensitization, heel be superimposed together to electrode, put after being fixed with clip
Enter in baking oven and heat, finally completes the assembling of device.
7. the preparation method of layer zinc oxide light anode according to claim 6, it is characterised in that:
The conductive substrates of solar battery light anode in the step (1) are FTO glass；
Tape thickness is 20~40 μm in the step (1), and the time that knifing is placed in air after completing is 5~15min；
Increase in the step (2) adhesive tape with a thickness of 40~80 μm, 200~300 DEG C of heat treatment temperature, 2~4h of time；
Electrolyte used in the step (4) has following composition: 0.1mol L-1LiI, 0.1mol L-1I2,0.6mol
L-11,2- dimethyl -3- propyl imidazole iodine, 0.45mol L-1N- methyl sheet and imidazoles, solvent is methoxypropionitrile, gel
Agent is polyethylene oxide, and additive amount is the 10% of liquid electrolyte quality；
In the step (4), gel electrolyte needs first to carry out the pre-heat treatment before coating, it is therefore an objective to make it have certain stream
Dynamic property, heating temperature are 50~90 DEG C；Light anode is 80~100 DEG C with the heat treatment temperature after overlapping to electrode, the time 15
~30 minutes, the purpose for the arrangement is that in order to permeate gel electrolyte completely in porous electrode.
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